CN115894803A - Preparation method and application of single-ion-conduction solid polymer electrolyte - Google Patents
Preparation method and application of single-ion-conduction solid polymer electrolyte Download PDFInfo
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Abstract
The present application provides compositions useful for preparing solid polymer electrolytes, and in particular provides solid polymer electrolytes, methods of making the same, and corresponding uses. The solid polymer electrolyte according to the present application is polymerized from a composition comprising: an organoborate compound, comprising one or more unsaturated bonds; a crosslinking agent; a polymeric substrate; a solvated ionic liquid; and (photo) initiators. The solid polymer electrolyte is a single ion conduction electrolyte, has high ionic conductivity and high lithium ion transference number, can be prepared into a polymer electrolyte membrane with good oxidation stability, and has good practical application prospect.
Description
Technical Field
The present invention relates generally to the field of batteries, in particular electrolytes, and in particular to solid polymer electrolytes, in particular single ion conducting solid polymer electrolytes, methods of making, uses of, and batteries comprising the same.
Background
Lithium metal has an ultrahigh theoretical specific capacity (3860 mAh g) -1 ) It is considered to be a very potential anode material. The continued reaction of conventional commercial electrolytes with lithium metal results in continued consumption of lithium metal and electrolyte, resulting in reduced capacity and shorter cycle life. In addition, uneven lithium deposition on the surface of lithium metal in commercial electrolytes can lead to lithium dendrite growth and ultimately to cell shorting.
Solid electrolytes are generally considered to have higher safety and stability than electrolytes. The solid polymer electrolyte has the advantages of good flexibility, enhanced safety, lower interface impedance, easiness in processing and the like, and is suitable for large-scale application. However, most reported solid polymer electrolytes are bi-ionically conductive, both lithium ions and anions are free to move, and the lithium ions move much slower than anions due to coordination between the lithium ions and lewis basic sites of the polymer chains, and the Lithium Ion Transport Number (LITN) is typically below 0.5. And the anions can not be deposited on the electrode, and excessive anions are gathered on the surface of the positive electrode, so that concentration polarization is generated inside the battery, and a larger overpotential is caused, thereby limiting the improvement of the energy density and the power density of the lithium ion battery.
Therefore, there is a need to develop a solid polymer electrolyte capable of overcoming these drawbacks.
Disclosure of Invention
In a first aspect, the present application provides a composition for preparing a solid polymer electrolyte, comprising: an organoborate compound comprising one or more unsaturated bonds; a crosslinking agent; a polymeric substrate; a solvated ionic liquid; and a photoinitiator.
In a second aspect, the present application provides a solid polymer electrolyte obtained by polymerization from a composition according to the preceding description.
In a third aspect, the present application provides a method for preparing a solid polymer electrolyte, comprising the steps of:
mixing the components of the composition according to the present application to obtain a precursor solution; and initiating the polymerization of the precursor liquid by light irradiation to obtain the solid polymer electrolyte.
In a fourth aspect, the present application provides a method of making a battery, comprising:
mixing the components of the composition according to the present application to obtain a precursor solution;
pouring the precursor solution into a mold, and initiating polymerization by light irradiation to form an electrolyte membrane; and
the electrolyte membrane was interposed between a positive electrode and a negative electrode to obtain a battery.
In a fifth aspect, the present application provides a battery made according to the above method.
In a sixth aspect, the present application provides a battery comprising a solid polymer electrolyte according to the present application or a solid polymer electrolyte prepared according to the method of the present application.
In a seventh aspect, the present application provides the use of a solid polymer electrolyte according to the present application or a solid polymer electrolyte prepared according to the process of the present application in the preparation of a battery.
Drawings
The embodiments illustrated herein are further described below with reference to the accompanying drawings, but the drawings are only for the purpose of better understanding the concept of the present invention by those skilled in the art, and are not intended to limit the scope of the present invention.
FIG. 1 is a digital photograph of a solid polymer electrolyte membrane 1 in example 1;
FIG. 2 is a graph showing the ion conductivity of the solid polymer electrolyte membrane 1 in example 1;
FIG. 3 is a linear scanning voltammogram of the solid polymer electrolyte membrane 1 in example 1;
FIG. 4 is a graph showing a current/time test curve and impedance test curves before and after polarization of the solid polymer electrolyte membrane 1 in example 1;
fig. 5 is a magnification view of a battery using the solid polymer electrolyte membrane 1 of example 1, lithium iron phosphate as a positive electrode, and lithium metal as a negative electrode at different magnifications;
fig. 6 is a cycle diagram at 0.5C for a battery using the solid polymer electrolyte membrane 1 of example 1, lithium iron phosphate as a positive electrode, and lithium metal as a negative electrode;
fig. 7 is a cycle diagram at 0.5C for a battery using lithium iron phosphate as a positive electrode and lithium metal as a negative electrode in a commercial electrolyte (LB 001) in example 8;
fig. 8 is a cycle chart at 0.2C for a battery using the solid polymer electrolyte membrane 1 of example 1, nickel cobalt lithium manganate 811 as a positive electrode, and lithium metal as a negative electrode.
Fig. 9 is a cycle diagram at 0.2C for a battery using nickel cobalt lithium manganate 811 as a positive electrode and a lithium metal as a negative electrode in a commercial electrolyte (LB 001) in example 8.
Detailed description of the preferred embodiments
In the following, the inventive concept will be further elucidated on the basis of specific embodiments. However, the particular embodiments illustrated are for illustrative purposes only and are not intended to limit the scope of the invention. Those skilled in the art will recognize that a particular feature from any of the embodiments below may be used in any other embodiment without departing from the spirit of the invention.
The following description is provided to better define the present application and to guide those of ordinary skill in the art in the practice of the present application. Unless otherwise noted, terms are to be understood according to conventional usage by those of ordinary skill in the relevant art. All patent documents, academic papers, and other publications cited herein are incorporated by reference in their entirety.
Definition of
Where a range of numerical values is recited herein, the range includes the endpoints thereof, and all the individual integers and fractions within the range, and also includes each of the narrower ranges therein formed by all the various possible combinations of those endpoints and internal integers and fractions to form subgroups of the larger group of values within the stated range to the same extent as if each of those narrower ranges were explicitly recited. For example, the ultraviolet irradiation time of 10min to 15min means that the ultraviolet irradiation time may be 10min, 11min, 12min, 13min, 14min, 15min, or the like, and a range formed by the above.
As used herein, "about" or "approximately" means that the word approximately when modifying a numerical value means within 5% of the modified numerical value.
The term "optional" or "optionally" as used herein means that the subsequently described event or circumstance may, but need not, occur, and that the description includes instances where said event or circumstance occurs and instances where it does not.
As used herein, the term "organoboronate compound" refers to compounds containing one or more boron-oxygen (B-O) bonds, where the B atom employs an sp 2 And (3) hybridization.
The term "C1-C4 alkyl" as used herein includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl and the like.
The term "halogen" as used herein includes fluorine (F), chlorine (Cl), bromine (Br) and iodine (I).
As used herein, an "acrylate functional group" is a group as shown in formula a, wherein x represents a connection to an adjacent atom in the compound.
In the process of developing a new solid polymer electrolyte, the inventors of the present invention unexpectedly found that a solid polymer electrolyte prepared from a composition comprising an organoborate compound having an unsaturated bond (e.g., an olefinic bond), a crosslinking agent, a polymer substrate, a solvated ionic liquid, and a photoinitiator has excellent properties such as high ionic conductance, high cation transference number, and good oxidation stability.
Accordingly, in a first aspect, the present application initially provides a composition for preparing a solid polymer electrolyte, comprising: an organoborate compound having an unsaturated bond (e.g., an olefinic bond), a crosslinker, a polymer substrate, a solvating ionic liquid, and a photoinitiator. The composition according to the present application can give a solid polymer electrolyte by polymerization, particularly by photo-irradiation polymerization.
The components used in the composition according to the present application are described in detail below.
Organic borate compounds
As used herein, the term "organoboronate compound" refers to compounds having one or more (e.g., 1, 2, or 3) B-O bonds, where the B atom is sp 2 And (3) hybridization. Suitable organoborate compounds herein also contain one or more, preferably one, unsaturated bond. Preferably, the unsaturated bond is an olefinic bond, i.e. a carbon-carbon double bond.
Thus, preferably, the organoboronate compounds used herein may be selected from compounds represented by formula 1 and combinations thereof:
wherein R is 1 And R 2 May be the same or different and may be independently selected from-H, C1-C4 alkyl, halogen. In a preferred embodiment, R 1 And R 2 Can be selected from-H, -CH 3 and-F.
In a preferred embodiment, the organoborate compound can be selected from the group consisting of bis-fluoroallylboronic acid pinacol ester, allylboronic acid pinacol ester, or a combination thereof.
A single ion conducting form of solid polymer electrolyte can be achieved using the compositions of the present application as opposed to the common dual ion conducting form of solid polymer electrolyte. The inventors of the present invention have discovered that organic borate compounds, as a lewis acid, can be used as an anion acceptor to undergo lewis acid-base interaction with an anion to immobilize the anion on the polymer backbone of the composition or electrolyte. Along with the fixation of anions, cations such as lithium ion migration number (LITN) in the single-ion conducting electrolyte are improved, and the concentration polarization phenomenon of the anions can be inhibited, so that lower internal resistance and higher discharge voltage of the battery are obtained, and the rapid charging capability of the battery is improved. Fixing anions in the electrolyte may also facilitate uniform distribution and deposition of lithium ions on the surface of the lithium negative electrode.
Advantageously, the organoboronate compound can be 1wt% to 25wt%, such as 10wt% to 20wt%, for example, about 1wt%, 5wt%, 10wt%, 15wt%, 20wt%, or 25wt% of the composition.
Crosslinking agent
The crosslinking agent used herein may be a compound containing two or more acrylate functional groups per molecule.
In a preferred embodiment, the crosslinking agent is selected from the group consisting of compounds represented by formula 2, compounds represented by formula 3, and compounds represented by formula 4, and combinations thereof:
wherein m is an integer of 1 to 10, and n is an integer of 1 to 10.
Among them, the compound represented by formula 2 is also referred to as pentaerythritol tetraacrylate (monomer), the compound represented by formula 3 is also referred to as fluoropentaerythritol tetraacrylate (monomer), and the compound represented by formula 4 is also referred to as fluoroboric triacrylate (monomer),
the crosslinking agent comprises 1wt% to 15wt%, such as 1wt% to 10wt%, such as about 1wt%, 3wt%, 5wt%, 8wt%, 10wt%,12 wt%, or 15wt% of the composition, and the like.
Polymer substrate
The polymeric substrate used in this application serves as a support and may therefore also be referred to as a polymeric support substrate. The polymeric substrate may be selected from the group consisting of polyethylene oxide, polypropylene carbonate, polyethylene carbonate, polyacrylonitrile, polymethacrylate, polyvinylidene fluoride-hexafluoropropylene, polyvinylidene fluoride-trifluoroethylene, lithiated perfluorosulfonic acid resins, and combinations thereof.
Advantageously, the polymer base comprises from 5wt% to 25wt%, such as from 10wt% to 20wt% of the composition. For example, the polymer comprises, for example, 5wt%, 7.5wt%, 10wt%,12.5wt%, 5wt%, 17.5wt%, 20wt%, 22.5wt%, or 25wt% of the composition, and the like.
Solvated ionic liquids
The solvated ionic liquids used in this application comprise a lithium salt and an organic solvent. Specifically, the solvated ionic liquid is obtained by completely dissolving a lithium salt in an organic solvent.
The inventor of the invention finds that the solvated ionic liquid has good thermal stability and chemical stability, and can play a role of a plasticizer, thereby improving the ionic conductivity of an electrolyte and the interfacial wettability of an electrode.
The lithium salt may be an electrolyte salt. In a preferred embodiment, the lithium salt is selected from the group consisting of lithium bistrifluoromethylsulfonyl imide, lithium bisfluorosulfonyl imide and combinations thereof.
The organic solvent may be selected from the group consisting of triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether and combinations thereof.
In preferred solvating ionic liquids, the molar ratio of lithium salt and organic solvent may be about 1.
The solvated ionic liquid comprises 55wt% to 75wt% of the composition, e.g., 60wt% to 70wt%, such as about 55wt%, 57.5wt%, 60wt%, 62.5wt%, 65wt%, 67.5wt%, 70wt%, 72.5wt%, 75wt%, or the like.
Photoinitiator
The photoinitiator used in the present application is not particularly limited in principle as long as it can absorb energy in the ultraviolet region (250 nm to 420 nm) or visible region (400 nm to 800 nm) to initiate polymerization, crosslinking and curing of the monomers. In a preferred embodiment, the photoinitiator is a compound that initiates polymerization of the monomer to crosslink and cure upon irradiation in the ultraviolet region. For example, the photoinitiator used in the present application may be a compound which initiates polymerization of monomers to crosslink and cure upon irradiation with 365nm ultraviolet light.
In a particularly preferred embodiment, the photoinitiator may be selected from 2, 2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone, phenylbis (2, 4, 6-trimethylbenzoyl) phosphine oxide, and combinations thereof.
The photoinitiator comprises 1wt% to 5wt%, such as 2wt% to 4wt%, such as about 1wt%, 2wt%, 3wt%, 4wt%, or 5wt%, etc., of the total of the organoborate compound and the crosslinking agent.
Thus, in a second aspect, the present application provides a solid polymer electrolyte obtained by polymerization from the composition described above.
Accordingly, in a third aspect, the present application provides a method of preparing a solid polymer electrolyte, the method comprising the steps of:
mixing the components of the composition according to the present application to obtain a precursor solution; and initiating the polymerization of the precursor liquid by light irradiation to obtain the solid polymer electrolyte.
The method may further comprise the step of dissolving the lithium salt completely in an organic solvent to obtain a solvated ionic liquid prior to the step of mixing. Specifically, the lithium salt and the organic solvent are mixed in a molar ratio of 1.
In the mixing step of the components, the organic borate compound, the crosslinking agent, the polymer substrate, the solvated ionic liquid and the photoinitiator are mixed uniformly in proportion. Here, the order of addition is not particularly limited.
In the precursor liquid polymerization step, ultraviolet light or visible light with proper wavelength is adopted for the selected photoinitiator for irradiation, and the precursor liquid obtained in the mixing step is polymerized and cured. For example, the precursor solution may be irradiated with 365nm ultraviolet light for a certain period of time for 2, 2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone, phenylbis (2, 4, 6-trimethylbenzoyl) phosphine oxide, and combinations thereof to polymerize and cure the precursor solution. The appropriate (uv) irradiation time can be selected at an appropriate power, for example 10min to 15min, as required.
According to the required shape, the precursor liquid can be cast in a mold (such as a mold made of polytetrafluoroethylene), and after photoinitiation polymerization, solid polymer electrolytes with different shapes, such as electrolyte membranes, can be obtained.
In a fourth aspect, the present application provides a method of making a battery, comprising:
mixing the components of the composition according to the present application to obtain a precursor solution;
pouring the precursor solution into a mold, and initiating polymerization by light irradiation to form an electrolyte membrane; and
the electrolyte membrane was interposed between a positive electrode and a negative electrode to obtain a battery.
As above, the method may further comprise the step of completely dissolving the lithium salt in the organic solvent to obtain a solvated ionic liquid before the step of mixing. Specifically, the lithium salt and the organic solvent are mixed in a molar ratio of 1.
In the mixing step of the components, the organic borate compound, the crosslinking agent, the polymer substrate, the solvated ionic liquid and the photoinitiator are mixed uniformly in proportion. Here, the order of addition is not particularly limited.
In the precursor liquid polymerization step, ultraviolet light or visible light with proper wavelength is adopted for the selected photoinitiator for irradiation, and the precursor liquid obtained in the mixing step is polymerized and cured. For example, for 2, 2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone, phenylbis (2, 4, 6-trimethylbenzoyl) phosphine oxide, and combinations thereof, the precursor can be irradiated under 365nm ultraviolet light for a period of time to polymerize and cure the precursor. For example, a suitable (uv) irradiation time may be selected at a suitable power, e.g. 10min to 15min, as required.
In some embodiments, the battery may be a lithium battery.
In some embodiments, the positive electrode may comprise an active material selected from the group consisting of: lithium iron phosphate, lithium manganate, lithium cobaltate, lithium nickel cobalt manganate and combinations thereof.
In some embodiments, the negative electrode may be a lithium sheet.
In some embodiments, a battery is assembled by weighing a positive electrode active material, acetylene black, and a binder (e.g., PVDF) (the mass ratio of the three may be, for example, 8.
The present application thus also provides, in a further aspect, batteries, in particular lithium batteries, made therefrom.
In another aspect, the present application also provides a battery comprising a solid polymer electrolyte according to the present application or a solid polymer electrolyte prepared according to the method of the present application.
Accordingly, the present application provides in a further aspect the use of a solid polymer electrolyte according to the present application or a solid polymer electrolyte prepared according to the process of the present application in the preparation of a battery.
To summarize, the inventions of the present application provide one or more of the following advantages:
the organic borate compound selected by the invention is simple, and is used as a Lewis acid anion receptor to interact with lithium salt anions so as to fix anions on a polymer framework, increase the lithium ion mobility of electrolyte, inhibit concentration polarization phenomenon and reduce internal resistance of a battery;
according to the invention, anions are fixed by the organic borate compound serving as an anion receptor, so that the corrosion of the anions to the positive electrode material and the current collector is reduced, the high-pressure resistance of the electrolyte is improved, and the stable circulation of the high-pressure positive electrode material is realized;
the electrolyte membrane prepared by the method is a self-supporting electrolyte membrane, so that the risk of liquid leakage is avoided, and the safety performance is improved;
the solvating ionic liquid adopted by the invention has good thermal stability and chemical stability, and is used as a plasticizer, so that the ionic conductivity of the electrolyte and the interface wettability of the counter electrode are improved;
according to the invention, by adding the polymer substrate and the cross-linking agent, a stable cross-linking network with high mechanical strength is formed in the electrolyte, the chemical stability and the electrochemical stability of the electrolyte are improved, the growth of lithium dendrite of a negative electrode is effectively inhibited, and the interface stability and the long cycle performance are improved;
the method has the advantages of simple operation, high initiation efficiency, short time consumption and easy industrial large-scale preparation.
Examples
In order to better illustrate the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to specific examples and comparative examples. The test methods used in the following examples are all conventional methods unless otherwise specified; the materials, reagents and the like used are, unless otherwise specified, commercially available reagents and materials. The following examples are for the purpose of illustration only and are not intended to limit the scope of the present application.
Example 1
Lithium bistrifluoromethylsulfonyl imide (LiTFSI) and tetraglyme (G) were placed in a glove box filled with argon 4 ) Stirring and dissolving for 24h to prepare solvated ionic liquid (G) 4 -TFSI); polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP), pentaerythritol tetraacrylate (PETA), allylboronic Acid Pinacol Ester (AAPE), and solvating ionic liquid (G) 4 -TFSI) and 2-hydroxy-2-methyl-1-phenyl-1-acetone (HMPP) are stirred and dissolved into a reaction precursor solution 1; and (3) casting the precursor solution 1 into a polytetrafluoroethylene mold, and irradiating for 15min under 365nm ultraviolet light for photo-initiated polymerization to obtain the electrolyte membrane 1. A digital photograph of the electrolyte membrane 1 is shown in fig. 1. Placing the electrolyte membrane 1 in lithium iron phosphate or lithium nickel cobalt manganese 811 (LiNi) 0.8 Mn 0.1 Co 0.1 O 2 ) Is justThe electrode and the lithium metal negative electrode are assembled to form the all-solid-state battery 1.
The formulation ratios of the components of the composition for preparing a solid polymer electrolyte in example 1 are as follows.
* The monomer weight refers to the sum of the weight of the crosslinking agent and the organoboronate compound as monomers, as follows.
Example 2
Lithium bis (fluorosulfonylimide) (LiFSI) and tetraglyme (G) were placed in a glove box filled with argon 4 ) Stirring and dissolving for 24h to prepare solvated ionic liquid (G) 4 -FSI); polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP), pentaerythritol tetraacrylate (PETA), allylboronic Acid Pinacol Ester (AAPE), the solvating ionic liquid (G) 4 -TFSI) and 2-hydroxy-2-methyl-1-phenyl-1-propanone (HMPP) were dissolved with stirring to form a reaction precursor solution 2; and (3) casting the precursor solution 2 into a polytetrafluoroethylene mold, and irradiating for 15min under 365nm ultraviolet light for photo-initiated polymerization to obtain the electrolyte membrane 2. Placing the electrolyte membrane 2 in lithium iron phosphate or lithium nickel cobalt manganese 811 (LiNi) 0.8 Mn 0.1 Co 0.1 O 2 ) And an all-solid-state battery is assembled between the positive electrode and the lithium metal negative electrode.
The formulation ratios of the components of the composition for preparing a solid polymer electrolyte in example 2 are as follows.
Example 3
Lithium bistrifluoromethylsulfonyl imide (LiTFSI) and tetraglyme (G) were placed in a glove box filled with argon 4 ) Stirring and dissolving for 24h to prepare solvated ionic liquid (G) 4 -TFSI); polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP), pentaerythritol tetraacrylate (PETA), bis (fluoro) allylboronic acid pinacol ester (2F-AAPE, R in formula 1) 1 ＝R 2 = F), solvated ionic liquid (G) 4 -TFSI) and 2-hydroxy-2-methyl-1-phenyl-1-propanone (HMPP) were dissolved with stirring to form a reaction precursor solution 3; and (3) casting the precursor solution 3 into a polytetrafluoroethylene mold, and irradiating for 15min under 365nm ultraviolet light for photo-initiated polymerization to obtain the electrolyte membrane 3. Placing the electrolyte membrane 3 in lithium iron phosphate or lithium nickel cobalt manganese 811 (LiNi) 0.8 Mn 0.1 Co 0.1 O 2 ) And a solid-state battery is assembled between the positive electrode and the lithium metal negative electrode.
The formulation of each component used to prepare the solid polymer electrolyte in example 3 is shown in the following table.
Example 4
Lithium bistrifluoromethylsulfonyl imide (LiTFSI) and tetraglyme (G) in a glove box filled with argon 4 ) Stirring and dissolving for 24h to prepare solvated ionic liquid (G) 4 -TFSI); polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP), hexadecyl fluoro pentaerythritol tetraacrylate (16F-PETA, formula 3, m = 1), allyl boronic acid pinacol ester (AAPE), solvating ionic liquid (G) 4 -TFSI) and 2-hydroxy-2-methyl-1-phenyl-1-propanone (HMPP) are dissolved with stirring to form a reaction precursor solution 4; and (3) casting the precursor solution 4 into a polytetrafluoroethylene mold, and irradiating for 15min under 365nm ultraviolet light for photo-initiated polymerization to obtain the electrolyte membrane 4. Placing the electrolyte membrane 4 in lithium iron phosphate or lithium nickel cobalt manganese 811 (LiNi) 0.8 Mn 0.1 Co 0.1 O 2 ) And an all-solid-state battery is assembled between the positive electrode and the lithium metal negative electrode.
The formulation of each component used to prepare the solid polymer electrolyte in example 4 is as follows.
Example 5
Lithium bis (trifluoromethylsulfonyl) imide (LiTFS) was placed in a glove box filled with argonI) And tetraethylene glycol dimethyl ether (G) 4 ) Stirring and dissolving for 24h to prepare solvated ionic liquid (G) 4 -TFSI); polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP), hexadecyl fluoro pentaerythritol tetraacrylate (16F-PETA, m =1 in formula 3), bis (fluoro) allylboronic acid pinacol ester (2F-AAPE, R in formula 1) 1 ＝R 2 = F), the solvated ionic liquid (G) 4 -TFSI) and 2-hydroxy-2-methyl-1-phenyl-1-propanone (HMPP) were dissolved with stirring to form a reaction precursor solution 5; and (3) casting the precursor solution 5 in a polytetrafluoroethylene mold, and irradiating for 15min under 365nm ultraviolet light for photo-initiated polymerization to obtain the electrolyte membrane 5. Placing the electrolyte membrane 5 in lithium iron phosphate or lithium nickel cobalt manganese 811 (LiNi) 0.8 Mn 0.1 Co 0.1 O 2 ) And an all-solid-state battery is assembled between the positive electrode and the lithium metal negative electrode.
The formulation of each component used to prepare the solid polymer electrolyte in example 5 is shown in the following table.
Example 6
Lithium bistrifluoromethylsulfonyl imide (LiTFSI) and tetraglyme (G) were placed in a glove box filled with argon 4 ) Stirring to dissolve for 24h to prepare solvated ionic liquid (G) 4 -TFSI); polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP), dodecafluoroboric triacrylate (12F-TBC, n =1 in formula 4), allylboronic Acid Pinacol Ester (AAPE), solvated ionic liquid (G) 4 -TFSI) and 2-hydroxy-2-methyl-1-phenyl-1-propanone (HMPP) are dissolved with stirring to form a reaction precursor solution 6; and (3) casting the precursor solution 6 into a polytetrafluoroethylene mold, and irradiating for 15min under 365nm ultraviolet light for photo-initiated polymerization to obtain the electrolyte membrane 6. Placing the electrolyte membrane 6 in lithium iron phosphate or lithium nickel cobalt manganese 811 (LiNi) 0.8 Mn 0.1 Co 0.1 O 2 ) And an all-solid-state battery is assembled between the positive electrode and the lithium metal negative electrode.
The formulation of each component used to prepare the solid polymer electrolyte in example 6 is shown in the following table.
Example 7
Lithium bistrifluoromethylsulfonyl imide (LiTFSI) and tetraglyme (G) were placed in a glove box filled with argon 4 ) Stirring to dissolve for 24h to prepare solvated ionic liquid (G) 4 -TFSI); polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP), dodecafluoroboric triacrylate (12F-TBC, n =1 in formula 4), bis (fluoroallylboronic acid) pinacol ester (2F-AAPE, R in formula 1) 1 ＝R 2 = F), solvated ionic liquid (G) 4 -TFSI) and 2-hydroxy-2-methyl-1-phenyl-1-propanone (HMPP) are dissolved with stirring to form a reaction precursor solution 7; and casting the precursor solution 7 into a polytetrafluoroethylene mold, and irradiating for 15min under 365nm ultraviolet light for photo-initiated polymerization to obtain the electrolyte membrane 7. The electrolyte membrane 7 was placed in lithium iron phosphate or lithium nickel cobalt manganese 811 (LiNi-Li) 0.8 Mn 0.1 Co 0.1 O 2 ) And an all-solid-state battery is assembled between the positive electrode and the lithium metal negative electrode.
The formulation of each component used to prepare the solid polymer electrolyte in example 7 is shown in the following table.
Example 8
The lithium metal solid-state battery obtained in the above embodiment is subjected to an electrical performance test, which mainly includes:
(1) The battery assembled in example 1 and using lithium iron phosphate as a positive electrode and lithium metal as a negative electrode was cycled 5 cycles at 0.1c,0.2c,0.5c,1c,2c, and 3c magnifications in an environment of 25 ℃ to obtain a graph of the relationship between specific capacity and magnification.
For a battery with lithium iron phosphate as a positive electrode and lithium metal as a negative electrode, the cycle performance is tested at 0.5C rate in an environment of 25 ℃, and the cycle performance is compared with a commercial electrolyte (LB 001) under the same test conditions;
for a battery with nickel cobalt lithium manganate 811 as the positive electrode and lithium metal as the negative electrode, the cycle performance was tested at 0.2C rate in an environment of 25 ℃, and compared with a commercial electrolyte (LB 001) under the same test conditions.
The formulation of the comparative electrolyte composition is shown in the following table.
| Composition of LB001 | Lithium salt LiPF 6 | Solvent EC/DMC |
| Content of the components | 1mol/L | 1:1Vol％ |
And (3) performance test results:
the solid polymer electrolyte in example 1 was an anion receptor type single ion conductive polymer electrolyte, which showed 0.7 × 10 at 25 ℃ -3 S cm -1 Is able to satisfy the cell test at room temperature (see fig. 2). In addition, it can be seen from the linear sweep voltammetry test that the oxidation stable potential of the solid polymer electrolyte can reach 5.4V (see fig. 3), and the solid polymer electrolyte can be matched with a positive electrode (such as nickel cobalt lithium manganate 811) with a high working potential. The time/current test and the impedance test results before and after polarization are shown in fig. 4, the solid polymer electrolyte shows a high lithium ion transport number of 0.71, the resistance of the electrolyte before and after polarization does not change, and the curve semi-circle does not change much, which indicates that the solid polymer electrolyte effectively inhibits concentration polarization caused by anion transfer.
The rate test result of the battery in which the lithium iron phosphate in example 1 is the positive electrode and the lithium metal is the negative electrode shows that the solid polymer electrolyte has good capacity performance even under higher rate, and has practical application prospects (see fig. 5). In addition, the battery can stably cycle for 480 cycles at a rate of 0.5C, the capacity retention rate is 85%, and the coulombic efficiency is above 99% (see fig. 6). It was confirmed that the lithium metal battery assembled with the gel polymer electrolyte in example 1 can obtain excellent cycle stability. Under the same conditions, the coulombic efficiency is kept below 98% in the battery circulation process of the reference commercial electrolyte LB001, and is obviously reduced at 500 circles, so that serious overcharge occurs (see FIG. 7).
In the battery of example 1 in which lithium nickel cobalt manganese 811 was used as the positive electrode and lithium metal was used as the negative electrode, the specific capacity reached 171mAh g at 0.2C -1 And the stable cycle was maintained for 200 cycles with a capacity retention of 75% (see fig. 8). It was confirmed that the lithium metal battery assembled with the solid polymer electrolyte in example 1 can still obtain excellent capacity expression and cycle stability for a high-voltage positive electrode. Whereas under equivalent conditions, the cell failed short circuit with 25 cycles of the reference commercial electrolyte LB001 (see fig. 9).
Therefore, the solid polymer electrolyte according to the present application can be used in a secondary battery such as a lithium metal battery, as an anion receptor type single ion conducting polymer electrolyte, and by selecting a simple borate compound as a lewis acid anion receptor to interact with lithium salt anions so as to fix the anions on a polymer skeleton, the transference number of lithium ions of the electrolyte is increased, the concentration polarization phenomenon is inhibited, the internal resistance of the battery is reduced, meanwhile, the corrosion of the anions on a positive electrode material and a current collector is reduced, the high pressure resistance of the electrolyte is improved, the stable circulation of the lithium metal battery is realized, and good battery performance can be obtained by matching the high pressure positive electrode material.
All publications mentioned or cited herein are incorporated by reference, including all figures and tables, unless expressly indicated otherwise.
It is understood that the examples and embodiments described herein are for illustrative purposes only and that various modifications or changes in light thereof will be suggested to persons skilled in the art and are to be included within the spirit and purview of this application. Furthermore, any element or limitation of any invention or implementation disclosed herein can be combined with any and/or all other elements or limitations disclosed herein (alone or in any combination) or any other invention or embodiment disclosed herein, and the invention contemplates and is not limited to all such combinations.
Claims (10)
1. A composition for preparing a solid polymer electrolyte comprising:
an organoborate compound comprising one or more unsaturated bonds;
a crosslinking agent;
a polymeric substrate;
a solvated ionic liquid; and
a photoinitiator.
2. The composition of claim 1 wherein the organoborate compound is selected from the group consisting of compounds represented by formula 1 and combinations thereof:
wherein R is 1 And R 2 Are identical or different and are each selected from-H, C1-C4 alkyl, halogen, preferably from-H and-F; and/or
The crosslinking agent is a compound containing two or more acrylate functional groups per molecule; preferably, the crosslinking agent is selected from the group consisting of compounds represented by formula 2, compounds represented by formula 3, and compounds represented by formula 4, and combinations thereof:
wherein m is an integer of 1 to 10, and n is an integer of 1 to 10;
optionally, the organoborate compound comprises 1wt% to 25wt%, such as 10wt% to 20wt%, of the composition;
optionally, the crosslinking agent comprises 1wt% to 15wt%, such as 1wt% to 10wt% of the composition.
3. The composition of claim 1, wherein the polymeric substrate is selected from the group consisting of polyethylene oxide, polypropylene carbonate, polyethylene carbonate, polyacrylonitrile, polymethacrylate, polyvinylidene fluoride-hexafluoropropylene, polyvinylidene fluoride-trifluoroethylene, lithiated perfluorosulfonic acid resins, and combinations thereof;
optionally, the polymer substrate comprises 5wt% to 25wt%, such as 10wt% to 20wt% of the composition; and/or
The solvating ionic liquid comprises a lithium salt, preferably an electrolyte salt, particularly preferably selected from lithium bistrifluoromethylsulfonyl imide, lithium bisfluorosulfonyl imide and combinations thereof, and an organic solvent, preferably selected from triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether and combinations thereof;
optionally, the solvated ionic liquid comprises from 55wt% to 75wt%, e.g., from 60wt% to 70wt%, of the composition, preferably the molar ratio of the lithium salt and the organic solvent is from about 1; and/or
Preferably, the photoinitiator is selected from the group consisting of 2, 2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone, phenylbis (2, 4, 6-trimethylbenzoyl) phosphine oxide, and combinations thereof;
optionally, the initiator comprises from 1wt% to 5wt%, for example from 2wt% to 4wt%, of the total of the organoboronate compound and the crosslinker.
4. A solid polymer electrolyte obtained by polymerization from the composition according to any one of claims 1 to 3.
5. A method for preparing a solid polymer electrolyte comprising the steps of:
mixing the components of the composition according to any one of claims 1 to 3 to obtain a precursor solution; and
and initiating the polymerization of the precursor solution by light irradiation to obtain the solid polymer electrolyte.
6. A method of making a battery comprising:
mixing the components of the composition as defined in any one of claims 1 to 3 to obtain a precursor liquid;
pouring the precursor solution into a mold, and initiating polymerization by light irradiation to form an electrolyte membrane; and
the electrolyte membrane was interposed between a positive electrode and a negative electrode to obtain a battery.
7. The production method according to claim 6, wherein:
the positive electrode of the battery is selected from the following active materials: lithium iron phosphate, lithium manganate, lithium cobaltate, lithium nickel cobalt manganate, and combinations thereof; and/or
The negative electrode of the battery is a lithium sheet; and/or
The battery is a lithium battery.
8. A battery produced by the production method according to claim 6 or 7.
9. A battery comprising the solid polymer electrolyte according to claim 4 or the solid polymer electrolyte produced by the production method according to claim 5.
10. Use of the composition according to any one of claims 1 to 3, the solid polymer electrolyte according to claim 4, or the solid polymer electrolyte produced by the production method according to claim 5 for producing a battery.
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|---|---|---|---|---|
| US20130059210A1 (en) * | 2011-09-05 | 2013-03-07 | Samsung Sdi Co., Ltd. | Electrolyte for rechargeable lithium battery and rechargeable lithium battery including same |
| US20140079987A1 (en) * | 2011-05-09 | 2014-03-20 | Shin-Kobe Electric Machinery Co., Ltd. | Nonaqueous Electrolyte Solution and Lithium Ion Battery |
| WO2020102907A1 (en) * | 2018-11-21 | 2020-05-28 | HYDRO-QUéBEC | Polymeric compositions comprising at least two lithium salts and the use of same in electrochemical cells |
| CN112164824A (en) * | 2020-09-07 | 2021-01-01 | 五邑大学 | Anion receptor type single-ion conductor flame-retardant gel polymer electrolyte and preparation method thereof |
| CN114085325A (en) * | 2021-10-29 | 2022-02-25 | 西安交通大学 | Ion-conducting semi-interpenetrating network polymer and preparation method and application thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140079987A1 (en) * | 2011-05-09 | 2014-03-20 | Shin-Kobe Electric Machinery Co., Ltd. | Nonaqueous Electrolyte Solution and Lithium Ion Battery |
| US20130059210A1 (en) * | 2011-09-05 | 2013-03-07 | Samsung Sdi Co., Ltd. | Electrolyte for rechargeable lithium battery and rechargeable lithium battery including same |
| WO2020102907A1 (en) * | 2018-11-21 | 2020-05-28 | HYDRO-QUéBEC | Polymeric compositions comprising at least two lithium salts and the use of same in electrochemical cells |
| CN112164824A (en) * | 2020-09-07 | 2021-01-01 | 五邑大学 | Anion receptor type single-ion conductor flame-retardant gel polymer electrolyte and preparation method thereof |
| CN114085325A (en) * | 2021-10-29 | 2022-02-25 | 西安交通大学 | Ion-conducting semi-interpenetrating network polymer and preparation method and application thereof |
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